Process for preparing alternating copolymers of butadiene and alpha-olefine and high molecular weight alternating copolymers

ABSTRACT

A PROCESS FOR PREPARING AN ALTERNATING COPOLYMER OF BUTADIENE AND A-OLEFINE IS DISCLOSED. SAID PROCESS COMPRISES CONTACTING BUTADIENE AND A-OLEFINE IN LIQUID PHASE WITH A CATALYST SYSTEM COMPRISING THE FIRST COMPONENT OF AN ORGANOALUMINUM COMPOUND HAVING THE GENERAL FORMULA ALR3 (R REPRESENTS A HYDROCARBON RADICAL), THE SECOND COMPONENT BEING A VANADIUM COMPOUND HAVING NO VANADIUM-HALOGEN LINKAGE AND THE THIRED COMPONENT BEING CHLORINE, BROMINE, IODINE, A COMPOUND THEREOF OR A MIXTURE OF THEM. THE COPOLYMERIZATION CONDITIONS SUCH AS TEMPERATURE, INITIAL MONOMER COMPOSITION, DILUENT ETC. ARE ALSO DISCLOSED. PHYSICAL PROPERTIES OF A NOVEL HIGH MOLECULAR WEIGHT ALTERNATING COPOLYMER OF BUTADIENE AND AN A-OLEFINE HAVING THE FORMULA CH2=CHR, WHEREIN R REPRESENTS A C1-C4 NORMAL OR BRANCHED CHAIN ALKYL RADICAL ARE ALSO DISCLOSED.

March 28, 1972 no KAWASAKI ETAL 3,652,518

\ mocrzss FOR PREPARING ALTERNATING COPOLYMERS OF BUTADIE'NE ANDd-OLEFINE AND HIGH MOLECULAR WEIGHT ALTERNATING COPOLYMERS Filed Dec.15, 1969 3 Sheets-Sheet 1 March 28, 1972 AKlHlRO KAWASAKI ETA!-3,652,513

PROCESS FOR PREPARING ALTERNATING COPQLYMERS 0F BUTADIENE AND -OLEFINEAND HIGH MOLECULAR WEIGHT ALTERNATING COPOLYMERS Filed Dec. 15, 1969 3Sheets-Sheet 2 3000 2000' I800 I500"I4 00 I200 I000 860 650 3500 2500I900 I700 I500 I300 II00 900 700 March 28, 1972 AKIHIRO KAWASAKI ETAL3,652,518

PROCESS FOR PREPARING ALTERNATING COPOLYMERS OF BUTADIENE AND d-OLEFINEAND HIGH MOLECULAR WEIGHT ALTERNATING COPOLYMERS Filed Dec. 15, 1969 5Sheets-Sheet L'- 3000 2000 I800 |6OO 1400 |2OO |OOO 800 650 3500 2500I900 I700 I500 I300 H00 900 700 mr'l United States Patent 3,652,518PROCESS FOR PREPARING ALTERNATING C0- POLYMERS OF BUTADIENE ANDa-OLEFINE AND HIGH MOLECULAR WEIGHT ALTERNAT- ING COPOLYMERS AkiliiroKawasaki, Ichihara-shi, Hiroaki Ueda, Chiha-shi, and Isao Maruyama,Ichihara-shi, Japan, assignors to Maruzen Petrochemical Co., Ltd.,Tokyo, Japan Filed Dec. 15, 1969, Ser. No. 884,871 Claims priority,application Japan, Dec. 26, 1968, 43/9 1,939; Mar. 22, 1969, 44/21,423;Apr. 15, 1969, 44/218,632

Int. Cl. C08d 1/14, 3/02 US. Cl. 260-853 9 Claims ABSTRACT OF THEDISCLOSURE A process for preparing an alternating copolymer of butadieneand a-olefine is disclosed. Said process comprises contacting butadieneand u-olefine in liquid phase with a catalyst system comprising thefirst component of an organoaluminum compound having the general formulaAIR, (R represents a hydrocarbon radical), the second component being avanadium compound having no vanadium-halogen linkage and the thirdcomponent being chlorine, bromine, iodine, a compound thereof or amixture of them. The copolymerization conditions such as temperature,initial monomer composition, diluent etc. are also disclosed. Physicalproperties of a novel high molecular weight alternating copolymer ofbutadiene and an a-olefine having the formula CH CHR, wherein Rrepresents a C -C normal or branched chain alkyl radical are alsodisclosed.

BACKGROUND OF THE INVENTION The present invention relates to newalternating copolymers of butadiene and a-olefine and to a process fortheir preparation.

Because of its chipping and cutting properties and its low skidresistance, the demand for cis-1.4 polybutadiene in the field ofautomobile tires is not so large as was expected at first. The defectshave been ascribed to its unbranched straight-chain structure. In orderto overcome these defects, many attempts have been made to producealternating copolymers of butadiene and a-olefine, for example,butadiene and propylene, butadiene and l-butene, etc. However, ingeneral, it is not easy to produce even a random copolymer of butadieneand a-olefine by an ionic catalyst.

For instance, German Pat. 1,173,254 claims a process for preparing acopolymer of conjugated diene and monoolefine using vanadium (V)oxychloride as the catalyst, but the examples do not show acopolymerization reaction of butadiene and propylene. German Pat.1,144,924 claims a process for preparing a copolymer of diene andethylene or propylene using a catalyst system consisting of a compoundof Ti, Zr, Ce, V, Nb, Ta, Cr, Mo or W in which the metal is at least inpart below a valency of 3. This patent shows the copolymerizationreaction of butadiene and ethylene by titaniumtetrachloride-phenylmagnesiumbromide, titanium tetrachloridelithiumaluminumhydride, titanium tetrachloridesodium dispersion,zirconium tetrachloride-tintetrabutyl andtetraoctyltitanate-phenylmagnesinmbromide catalyst systems in itsexamples, but a process for preparing a copolymer of butadiene andpropylene is not shown. Belgian Pat. 625,657 also describes a processfor preparing coand terpolymers of butadiene with ethylene and/ora-olefines using a catalyst system containing a hydrocarbon-solublevanadium compound and an organoaluminum compound containing more thanone organic group having strong sterical hindrance, e.g. 3-methylbutyl,cycloalkyl or cyclopentylmethyl, and it claims a process for preparingethylene-propylene-butadiene terpolymer. However, no example ofbutadiene-propylene copolymer is shown in it.

On the other hand, British Pat. 1,108,630 shows a process for preparinga rubbery random copolymer of butadiene and propylene by using a threecomponent catalyst system consisting of a trialkylaluminum, iodine and acompound having the general formula of TiBr CL wherein n is zero or aninteger of 1 to 4. A random copolymer of butadiene and propylene wasalso prepared by using a catalyst system consisting oftriethylaluminurn, titanium tetrachloride and polypropylene oxide.Polypropylene oxide was used as a randomizer and therefore a copolymerof butadiene and propylene prepared by the catalyst system oftriethylaluminum, and titanium tetrachloride was shown to be block-type(paper presented at 2nd Symposium on Polymer Synthesis, Tokyo, Oct. 5,1968, The Society of Polymer Science, Japan). British Pat, 1,026,615claims a process for preparing a random copolymer of butadiene andpropylene by forming a catalyst system of triethylaluminum and titaniumtetrachloride in the presence of propylene, and then adding butadiene tothe catalyst system. According to the patent, the propylene content ofthe copolymer was much higher than that of the copolymer prepared by thecatalyst formed after the monomers were mixed. This result isinconsistent with the result described in the above paper. Acopolymerization reaction of butadiene and propylene was also carriedout by using a catalyst system of triethylaluminum and titaniumtetrachloride prepared in propylene and the product was confirmed, byfractional precipitation test, to be a copolymer of butadiene andpropylene (Chemistry of High Polymers, The Society of Polymer Science,Japan, 20, 461 (1963)). The content of this paper corresponds to that ofthe above British patent, but there is no description in it showing thatthe copolymer should be a random copolymer of butadiene and propylene.

According to the method of British Pat. 982,708, a mixture containing-95 mole percent butadiene, the rest being 4-methyl-1-pentene, ispolymerized at a temperature in the range 0 to 30 C. by a catalystsystem which is the reaction product of vanadium (V) oxychloride withtriisobutylaluminum, an aluminumdialkyl monochloride or an aluminumsesquialkyl chloride. The microstructure of the copolymer is not shownin the patent. British Pat. 924,654 describes a process for preparing acopolymer of butadiene and propylene by using an Alfin catalyst. Thecopolymer showed a characteristic infra-red absorption band at 11.95microns. It was ascribed to tri-substituted ethylene structure.Therefore, the result does not support the assumption that the copolymershould be a random or alternating copolymer of butadiene and propylene.

Consequently, as far as the inventors know, there is no prior art inconnection with alternating copolymers of butadiene and a-olefine norfor a process for their preparation.

SUMMARY OF THE INVENTION In accordance with this invention, it has beendiscovered that by using a catalyst system the first component of whichcomprises an organoaluminum compound having the general formula of AlRwherein R is a hydrocarbon radical such as an alkyl, aryl or cycloalkylradical, the second component a vanadium compound having novanadium-halogen linkage and the third component being chlorine, achlorine containing compound, bromine, a bromine containing compound,iodine, an iodine containing compound or a mixture of them, alternatingcopolymers of butadiene and ot-olefine can be produced. The newalternating copolymers of this invention are in general rubber-like incharacter and may be used as polymeric plasticizers, in adhesives andcan be vulcanized with sulfur or a sulfur compound to produce vulcanizedelastomers. Although, contrary to our expectation the microstructure ofbutadiene units of all of these alternating copolymers were trans1.4-configuration, the glass transition temperature of these copolymerswas very low and they showed rubber-like elasticity. This resultcoincides with that of the alternating copolymer of butadiene andacrylonitrile. (Journal of Polymer Science, B7, 411 (1969)). Themicrostructure of butadiene unit of the copolymer was trans1.4-configuration, but the copolymer also showed rubber-like elasticity.

Vanadium compounds having no vanadium-halogen linkage are used as thesecond component of the catalyst system of the present invention. Suchvanadium compounds include vanadium alkoxides having the general formulaof V(OR) wherein R is a hydrocarbon radical such as an alkyl, aryl orcycloalkyl radical; vanadium oxyalkoxides having the general formula ofOV(OR) wherein R is a hydrocarbon radical such as an alkyl, aryl orcycloalkyl radical; vanadium complex compounds such asdicyclopentadienyl vanadium, cyclopentadienyl tetracarbonyl vanadium,vanadium, triacetylacetonate, vanadium oxydiacetylacetonate; vanadiumsalts of carboxylic acids such as vanadium oxydiacetate etc.

The chlorine containing compounds, bromine containing compounds andiodine containing compounds that are used as the third component of thecatalyst system of the present invention are the compounds of atransition element having the transition element-halogen linkage, suchas compounds of the general formula VX wherein X is chlorine, bromine oriodine, compounds of the general formula VOX wherein X is chlorine,bromine or iodine, compounds of the general formula OV(OR) X wherein Xis chlorine, bromine or iodine, R is a hydrocarbon radical such as analkyl, aryl or cycoalkyl and n is a number from 1 to 2, compounds of thegeneral formula wherein X is chlorine, bromine or iodine and n is anumber from 1 to 2, compounds of the general formula V(C H ),,X whereinX is chlorine, bromine or iodine and n is a number from 1 to 2,compounds of the general formula V(C H X wherein X is chlorine, bromineor iodine, compounds of the general formula OV(C H )X wherein X ischlorine, bromine or iodine, compounds of the general formula Ti(OR)wherein X is chlorine, bromine or iodine, R is a hydrocarbon radicalsuch as an alkyl, aryl or cycloalkyl and n is a number from 1 to 3,compounds of the general formula Ti(C H X wherein X is chlorine, bromineor iodine, compounds of the general formula Ti(C H )X wherein X ischlorine, bromine or iodine, compounds of the general formula Ti(C H Xwherein X is chlorine, bromine or iodine, compounds of the generalformula (C H )Ti(OR)X wherein X is chlorine, bromine or iodine and R isa hydrocarbon radical such as an alkyl, aryl or cycloalkyl, compounds ofthe general formula (C H )Ti(OR) X wherein X is chlorine, bromine oriodine and R is a hydrocarbon radical such as an alkyl, aryl orcycloalkyl, compounds of the general formula TiX wherein X is chlorine,bromine or iodine, compounds of the general formula Zr(OR X wherein X ischlorine, bromine or iodine and R is a hydrocarbon radical such as analkyl, aryl or cycloalkyl, compounds of the general formula Zr(OR) Xwherein X is chlorine, bromine or iodine and R is a hydrocarbon radicalsuch as an alkyl, aryl or cycloalkyl, compunds of the general formulaZrX wherein X is chlorine, bromine or iodine, compounds of the generalformula CrO X wherein X is chlorine, bromine or iodine, compounds of thegeneral formula WX wherein X is chlorine, bromine or iodine, thecompounds of the general formula of FeX wherein X is chlorine, bromineor iodine, compounds of the general formula of MoX wherein X ischlorine, bromine or iodine, etc. and compounds of the elements of Group11111, IVa, Va and VIa of Periodic Table having the chemical bondbetween the element and a halogen atom, such as the compounds of thegeneral formula BX -OR wherein X is chlorine, bromine or iodine and R isa hydrocarbon radical such as an alkyl, aryl or cycloalkyl, compounds ofthe general formula AlR,,X wherein X is chlorine, bromine or iodine, Ris a hydrocarbon radical such as an alkyl, aryl or cycloalkyl and n is anumber from 1 to 2, compounds of the general formula AlOX wherein X ischlorine, bromine or iodine, compounds of the general formula AlX -ORwherein X is chlorine, bromine or iodine and R is a hydrocarbon radicalsuch as an alkyl, aryl or cycloalkyl, compounds of the general formulaSnX, wherein X is chlorine, bromine or iodine, compounds of the generalformula NOX wherein X is chlorine, bromine or iodine, compounds of thegeneral formula PX wherein X is chlorine, bromine or iodine, compoundsof the general formula BiX wherein X is chlorine, bromine or iodine,compounds of the general formula SOX wherein X is chlorine, bromine oriodine, the halogenated alkane compounds such as tert-butyl chloride,tert-butyl bromide, tert-butyl iodide, sec-butyl chloride, sec-butylbromide, sec-butyl iodide, tetrachloromethane, tetrabromomethane,tetraiodomethane, compounds of the general formula RCOX wherein R is ahydrocarbon radical such as an alkyl, aryl or cycloalkyl radical and Xis chlorine, bromine or iodine, etc.

The a-olefine of the general formula CH =CHR wherein R is a normal chainor branched chain lower alkyl group or a phenyl group is used as amonomer. Examples of such a-olefines are propylene, l-butene, l-pentene,1- hexene, 4-methyl-1-pentene, styrene, etc.

Preparation of the alternating copolymer of butadiene and a-olefine iscarried out by contacting butadiene with a-olefine in liquid phase inthe presence of the catalyst system described above. Thecopolymerization reaction is generally carried out in the presence of aliquid organic diluent. Suitable diluents that can be used for thecopolymerization reaction include hydrocarbon, such as heptane, octane,isooctane, benzene, toluene, etc., halogenated hydrocarbon, such asmethylene chloride, methylene bromide, ethylene chloride, etc. or amixture of them. The temperature of the copolymerization reaction may bevaried from 100 C. to 50 C. and sufiicient pressure is employed to keepthe monomers in liquid phase. The molar ratio of butadiene to a-olefinein the initial monomer composition may be from 20:80 to :20 and moreusually be 50:50.

At the completion of the copolymerization reaction, the product isprecipitated and deashed with the aid of a methanol-hydrochloric acidmixture. The precipitated product is washed with methanol several timesand dried under vacuum. Thereafter the product is extracted with diethylether or with methyl ethyl ketone. The diethyl ether or methyl ethylketone soluble fraction is collected as an alternating copolymer ofbutadiene and a-olefine.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The following examplesillustrate the new alternating copolymers of butadiene and a-olefine andthe process for preparation thereof in accordance with this invention.

Examples 1-13 In these examples, the usual, dry, air-free technique wasemployed and 5 milliliters toluene, varying amounts of vanadium (V)oxytriethoxide (OV(OEt) solution in toluene (1 molar solution), 'varyingamounts of halogen or halogen containing compounds, varying amounts ofHHHHHHHH a a a1 2 s N s is n o N .fo 3 ow 2 32 on EN o N N 2 @W ab Nu EN o oo 2 oo i ofioooooz on N o N N NH Po l no 3 om fi ooaoooow o N m N NN o on S oo 2 5 moooio m oh @N m N N S 1 mo 3 ow o oonooom o4 mN o N N oE a o NA E H o o 2 oo Ev oooo 62 on @N o N N o E m o o4 E N o oo 3 oo Go moo m on MN m N N E ME ab NA E N o 5o 2 om o oNowo H on N m N N o N4oo 8 ow 35 3o m ma o oh N a N N .....:...............................mon No 2 oo 2 o fio oo me o on EN n N N o @W mb N4 E N o mo 8 owndiowoiookr oo @N m N N N NA 5o 3 om S c mNooo Eo 9N o N N o no 2 ow 252169 oo N n N N 4 02 wEEox oo oo 3:3 Ho 40 a 35s o 25 0 0o E5858 am 2 V 52 V 5 25 2 v 25 E E Show E E 22% E9 e 5M9? 5 5 38 am m 2 25 ll H83232223 35m ne oflw 292% m; ESEUEB aoseoom N momfi oo wewaonez Efifio 32Ma; Q noaboaoo MEQNEBQ.

N 35 2. Ru 0 0 5 0 5 0 5 5 2 3 3 4 4 5 6 7 triisobutyl aluminum solutionin toluene (1 molar solution) and a mixture of 2 milliliters liquidpropylene, 2- milliliters liquid butadiene and 2 milliliters toluenewere put successively in a 25 milliliter glass bottle held in a lowtemperature bath at -78 C. Thereafter the bottle was sealed and allowedto copolymerize at 30 C. for 16 hours. The product purified by theprocess described above was extracted successively with methyl ethylketone and diethyl ether. The methyl ethyl ketone soluble fraction andthe methyl ethyl ketone insoluble, diethyl ether soluble fraction 'wereboth collected as alternating copolymers of butadiene and propylene. Theformer fraction was a low molecular weight copolymer and the latterfraction was a high molecular weight copolymer whose intrinsic viscositywas higher than 0.1 dl./ g. in chloroform at C. The copolymers showedtacky and rubber-like properties.

The following results support the conclusion that the copolymer is analternating copolymer of butadiene and propylene.

(1) The composition of the copolymer according to the NMR analysissubstantially agrees with the calculated value for the 1:1 copolymer ofbutadiene and propylene. Copolymer compositions were determined bymeasuring the ratio of peak area at 4.651- of butadiene unit to that 25of doublet at 9.11-r and 9.207 of propylene unit.

(2) The copolymerization reaction gives 1:1 copolymer over a wide rangeof initial monomer composition.

(3) The copolymerization reaction gives 1:1 copolymer independently ofpolymerization time.

(4) Although the microstructure of butadiene unit in the copolymer istrans 1.4-configuration, the crystallization sensitive bands of trans1.4 polybutadiene at 1335 cmf 1235 cmf 1121 GEL-1, 1054 cm.- and 773cm.- do not appear in its infra-red spectrum.

This means at least that the length of the butadienebutadiene repeatingunit of the copolymer is not so long as to be detected by its infra-redspectrum.

(5) The 1155 cm.- band of propylene homopolymer is not shown in itsinfra-red spectrum and a new broad band appears at 1065 -cm:-

This means at least that the length of the propylenepropylene repeatingunit of the copolymer is not so long as to be detected by its infra-redspectrum.

(6) Two new bands at 890 cm. and 1640 cm.* are observed in the infra-redspectrum of the methyl ethyl ketone soluble fraction of the copolymer.The 890 cm." band may be ascribed to the CH out of plane vibration modeof the terminal CH C=CH group of the copolymer and the 1640 cm? band mayalso be ascribed to the C=C stretching mode of the group.

(7) The absorption band at 967 cm? corresponding to the CH out of planedeformation mode of trans 1.4 polybutadiene shifts to high frequencyside by about 5 cmf This result suggests the existence of abutadienepropylene unit in the copolymer.

FIG. 1 shows the NMR spectrum of the methyl ethyl ketone insoluble,diethyl ether soluble fraction of the alternating copolymer of butadieneand propylene. FIG. 2 shows the infra-red spectrum of the fraction.

The results are summarized in Table 1. As can be seen in Ref. 1 of Table1, the catalyst system involving no halogen compound gives noalternating copolymer of butadiene and propylene.

parts by weight of the methyl ethyl ketone insoluble, diethyl ethersoluble fraction of the alternating copolymer of butadiene and propyleneprepared by the method of above Example No. 3 were mixed on a laboratoryroll mixer, with 2 parts of sulphur, 5 parts of zinc 70 oxide, 1 part oftetramethyl thiuram disulfide, 1 part of 2,5-di-tert-butyl hydroquinone,40 parts of HAF carbon black. The mixture thus obtained was vulcanizedin a press for 20 minutes at C. Tensile Strength of the sample waskg./cm.

7 Examples 14-16 In these examples, the usual, dry, air-free techniquewas employed and milliliters toluene, 1.00 milliliter vanadium (V)oxytriethoxide (OV(OEt) solution in toluene (1 molar solution), amixture of varying amounts of triisobutylaluminum solution in toluene (1molar solution) and varying amounts of ethylaluminum dichloride ordiethylaluminum monochloride solution in toluene (1 molar solution) anda mixture of 2 milliliters liquid propylene, 2 milliliters liquidbutadiene and 2 milliliters toluene were put successively in a 25milliliter glass bottleheld in a low temperature bath at 78 C.Thereafter the bottle was sealed and allowed to copolymerize at -30 C.for 16 hours. The product purified by the proctoluene (1 molarsolution), varying amounts of halogen or halogen containing compound,2.5 milliliters triisobutylaluminum solution in toluene (1 molarsolution), 3 milliliters styrene and 2 milliliters liquid butadiene wereput successively in a milliliter glass bottle held in a low temperaturebath at 78 C. Thereafter the bottle was sealed and allowed tocopolymerize at C. for 16 hours. The product purified by the processdescribed above was extracted with diethyl ether. The diethyl ethersoluble fraction was collected as an alternating copolymer of butadieneand styrene. The alternating copolymer was a rubber-like elastomer.

The following results support the conclusion that the copolymer shouldbe an alternating copolymer of butadiene and styrene.

TABLE 3 Reaction Monomers 1 Catalysts 2 conditions Alter- Diluent,nating Example Sty BD toluene Ali-Bu; 0V(OEt) Halogen Temp. Time copoly-No. (ml.) (ml.) (ml.) soln. (ml) soln. (ml.) compound Ml. 0.) (hr.) mer(g.)

18 3 2 5 2. 5 1. 0 B1; 0.03 30 16 1.2 19 3 2 5 2. 5 1. tort-BUCI 0. 1330 16 0. 9 20 3 2 5 2. 5 1. 0 T1014 0. 30 30 16 1.1

1 Sty: styrene; BD: liquid butadiene. Ali-Bu; soln.: 1 molartriisobutylaiuminum solution in toluene; OV(OEt)3 soln.: 1 molar OV(OEt)solution in toluene; OV(OEt)3 soln.: 1 molar OV(OEt); solution intoluene; tcrt-BuCl: tert-butyl chloride; T1014: 1

molar TiCli solution in toluene.

ess described above was extracted successively with methyl ethyl ketoneand diethyl ether.

The results are summarized in Table 2. As can be seen in Ref. 2 and 3 ofTable 2, even when the molar ratio of Al to V is 2.5 :1, the catalystsystem of OV(OEt) and AlEt Cl or AlEtCl gives no alternating copolymerof butadiene and propylene.

l) The composition of the copolymer according to the NMR analysissubstantially agrees well with the calculated value for the 1:1copolymer of butadiene and styrene.

(2) The copolymerization reaction gives 1:1 copolymer independently ofpolymerization time.

(3) The NMR spectrum of the copolymer shows a strong peak at 8.031-ascribing to the methylene groups TABLE 2 Alternating copolymer ReactionMonomers l Catalysts 3 conditions MEK insoluble, Diluent, diethyl etherExample Pr BD toluene Ali-Bu; OV(OEt) Halogen Temp. Time MEK solublesoluble N 0. (ml.) (ml.) (ml.) s0ln.(ml.) soln. (ml. compound Ml. C.)(hr.) traction (g.) fraction (g.)

14 2 2 5 2.0 1. 0 AlEtzCl 0. 5 30 16 0. 12 0.45 15 2 3 5 2. 25 1. 0AlEtCh 0. 25 30 16 0. 22 0. )3 16 2 2 5 2. 0 l. 0 AlEtClz 0. 5 30 160.15 0. 41 Ref. 2 2 2 5 1.0 AlEtzCl 2. 5 -30 16 0 0 Ref. 3 2 2 5 1. 0AlEtCls 2. 5 30 16 0 0 l Pr: liquid propylene; 13D: liquid butadiene.

Ali-Bu soln.: 1 molar triisobutylaluminum solution in toluene; OV(OEt)3soln.: 1 molar OV(OEt)3 solution in t0lueue;A1Et1Cl: 1 molar AlEtzClsolution in toluene; AlEtCh: 1 molar AlEtCl; solution in toluene.

Example 17 The usual, dry, air-free technique was employed and 5milliliters toluene, 0.085 milliliter chromyl chloride, 1.0 millilitervanadium (V) oxytriethoxide (OV(OEt) solution in toluene (1 molarsolution), 2.6 milliliters triisobutylaluminum solution in toluene (1molar solution), a mixture of 2 milliliters liquid propylene and 2milliliters toluene and 2 milliliters liquid butadiene were putsuccessively in a 25 milliliter glass bottle held in a low temperaturebath at 78 C. Thereafter the bottle was sealed and allowed tocopolymerize at -30 for 17.5 hours. The product purified by the processdescribed above was extracted with diethyl ether. The diethyl ethersoluble fraction was collected as an alternating copolymer of butadieneand propylene. The yield of the alternating copolymer was 1.63 g.Intrinsic viscosity of the copolymer was 0.3 dl./ g. in chloroform at 30C.

Examples 18-20 of butadiene-styrene repeating unit, but the 7.951 peakascribing to the methylene groups of 1.4 polybutadiene appears as a veryweak peak. The results substantially deny the existence ofbutadiene-butadiene repeating unit.

FIG. 3 shows the NMR spectrum of the alternating copolymer of butadieneand styrene. FIG. 4 shows the infra-red spectrum of the copolymer.

The results are summarized in Table 3.

Example 21 The usual, dry, air-free technique was employed and 7milliliters toluene, 0.08 milliliter chromyl chloride, 1.05 millilitersvanadium (V) oxytriethoxide (OV(OEt) solution in toluene (1 molarsolution), 2.6 milliliters triethylaluminum solution in toluene (1 molarsolution), 3 milliliters styrene and 2 milliliters liquid butadiene wereput successively in a 25 milliliter glass bottle held in a lowtemperature bath at 78 C. Thereafter the bottle was sealed and allowedto copolymerize at 30" for 17 hours. The product purified by the processdescribed above was extracted with diethyl ether. The diethyl ethersoluble fraction was collected as an alternating copolymer of 11 theprocess described above was extracted successively with methyl ethylketone and diethyl ether. The methyl ethyl ketone soluble fraction andthe methyl ethyl ketone insoluble, diethyl ether soluble fraction wereboth collected as an alternating copolymer of butadiene and aolefine.The former fraction was a low molecular weight copolymer and the latterone was a high molecular weight copolymer whose intrinsic viscosity washigher than 0.1 dL/g. in chloroform at 30 C. From their NMR and 4. Aprocess as claimed in claim 1, wherein the copolymerization reaction iscarried out in the presence of a diluent selected from a hydrocarbon, ahalogenated hydrocarbon or a mixture thereof.

5. A process as claimed in claim 1, wherein said organoaluminum compoundis triethylaluminum or triisobutylaluminum.

6. A process as claimed in claim 5, wherein said process is carried outat a temperature from 100 C. to 50 infra-red spectra these fractionswere determined to be C. in the presence of a diluent selected from ahydrocaran alternating copolymer of butadiene and ot-olefine, bon, ahalogenated or a mixture thereof using a feed respectively. compositionhaving a molar ratio of butadiene to said The results are summarized inTable 5. alpha-olefin of from :80 to 80:20.

TABLE 5 Alternating copolymer 3 Catalysts 1 Reaction MEK insoluble,diethyl Monomers conditions MEKsolubefraetlon other soluble fractionDiluent, Ali-Bu; V0 (0E0; A1613.

a-Olefine BD toluene soln. soln. OEtz Temp. Time Yield [1 Tg Yield [1;]T1;

Ex. No. (011.) (1111.) (mL) (ml.) (1111.) (mmol) C.) (hr-) (25.) (dl/g.G.) (g.) (dllg.) C.)

27 1-P(2.9) 2 9 1.0 0.3 0.21 16 0.3a 0.1 -75 1.00 0.4 74 2s4-M-1-P(3.3)...- 2 9 1.0 0.3 0.21 -30 16 0.41 0.1 -57 0. a4 0.3 --58 291-H (3.3 2 9 1.0 0.3 0.21 -30 16 0.38 0.1 -75 2.00 0.4 '10 1 LP: liquidl-pentene; *i-M-l-P: liquid 4-methyl-1-pentene; l-H: liquid l-hexene. 2AliBu; soln.: 1 molar triisobutylaluminurn solution in toluene; 0V(OEt)3soln.: 1 molar OV(OEt); solution in toluene. B [1;]: intrinsic viscosityin ehloroiorm at 30 0.; Tg: glass transition temperature.

What is claimed is:

1. A process for preparing a 1:1 copolymer of butadiene and analpha-olefin having alternating butadiene and alpha-olefin units, saidalpha-olefin having the general formula CH =CHR, wherein R represents aphenyl radical or a C to C normal or branched chain lower alkyl radical,which comprises contacting a mixture of butadiene and said alpha-olefinin liquid phase with a catalyst system comprising a first component ofan organoaluminum compound having the general formula AlR wherein R' isa hydrocarbon radical selected from the group consisting of alkyl, aryland cycloalkyl, a second component of a vanadium alkoxide having thegeneral formula V(OR) wherein R' is as defined above or a vanadiumoxyalkoxide having the general formula OV(OR') wherein R is as definedabove and a third component of chlorine, bromine, iodine, a compound ofa transition element having a linkage of a transition elementX, whereinX represents chlorine, bromine, or iodine, a compound of element ofGroup III-A, IV-A, VA or VIA of the Periodic Table having a linkage ofsaid elementX, wherein X is as defined above or a mixture thereof andwherein the atomic ratio of aluminum contained in said first component,vanadium contained in said second component and a halogen contained insaid third component is approximately 2-4.1/1/0.32.1.

2. A process as claimed in claim 1 wherein the molar ratio of butadieneto m-olefine in the initial monomer composition is within the range from20:80 to 80:20.

3. A process as claimed in claim 1, wherein the polymerizationtemperature is within the range from 100 C. to 50 C.

UNITED STATES PATENTS 3,457,250 7/1969 Gaeth 26094.3 3,506,632 4/1970Henderson 26085.3 3,317,496 5/1967 Natta et a1. 26088.2 3,407,18510/1968 Natta et a1. 26085.3 3,265,765 8/1966 Holden et a1. 260876FOREIGN PATENTS 716,173 8/1965 Canada 26094.3

JOSEPH L. SCHOFER, Primary Examiner R. A. GAITHER, Assistant ExaminerUS. Cl. X.R.

